Patent ES-295405-A1 (ES)
Title: Novel-1 (10)-13-alkyl gonenes and process for their manufacture
IPC: A61K31/567
Filed: 1964-01-16
Abstract: Novel 13-alkyl gonanes having attached to position 3 a keto group, containing at least one double bond located [alpha](#) with regard to said keto group, having a free or esterified hydroperoxy group attached to position 10 and possessing at C-17 either of the configurations wherein R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl or halogeno-lower alkynyl, and R1 is H or an acyl group are obtained in a process characterized in that a 3- keto-13-alkyl-gonane derivative containing a double bond between C-10 on the one hand and one of those carbon atoms which is located # with regard to the 3-Keto group on the other hand, and possessing the above defined configuration at C-17 is subjected to the action of a source of oxygen selected from oxygen, oxygencontaining gases and peroxides. Subsequently the following steps may be effected (a) esterification of a hydroxy group, particularly of that in the 10-hydroperoxy group (b) introduction of an additional double bond by dehydrogenation (c) oxidation of a hydroxy group to keto (d) dehydration of a 9-H-11- OH grouping to #9(11) (e) dihalogenation to 9[alpha], 11# - dihalogeno, or hydroxy - halogenation to 9[alpha]-halogeno-11#-hydroxy, of such a #9(11)- double bond. As source of oxygen, there may be employed hematoporphyrin or azoisobutyronitrile. A 13-alkyl-5(10)-gonene-3-one starting compound may be obtained by a Birch reduction of the corresponding 3-methoxy-13-alkyl- 1,3,5 (10)-gonatriene. A 3-keto-13-alkyl-5[alpha]- 1(10)-gonene starting compound may be obtained by deconjugating e.g. with an alkali metal acetylide, a corresponding 3-keto- 13- alkyl - 5[alpha] - 1(2) - gonene. A 13 - alkyl - ox- 1(10) - gonene - 3 - ol - 17 - one starting compound is obtained by oxidation of a 13-alkyl- 5[alpha] -1(10) - gonene - 17# - ol - 3 - one to form the corresponding 13-alkyl-5[alpha]-1(10)-gonene-3,17-dione followed by selective reduction. Pharmaceutical compositions having antigonadal or androgenic/anabolic activity and containing the above novel compounds are administered in tablets, solutions and suspensions.Novel 13-alkyl gonanes having attached to position 3 a keto group, containing at least one double bond located a(b) with regard to said keto group, having a free or esterified hydroperoxy group attached to position 10 and possessing at C-17 either of the configurations <FORM:1053214/C2/1> wherein R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl or halogeno-lower alkynyl, and R1 is H or an acyl group are obtained in a process characterized in that a 3-keto-13-alkyl -gonane derivative containing a double bond between C-10 on the one hand and one of those carbon atoms which is located b with regard to the 3-Keto group on the other hand, and possessing the above defined configuration at C-17 is subjected to the action of a source of oxygen selected from oxygen, oxygen-containing gases and peroxides. Subsequently the following steps may be effected (a) esterification of a hydroxy group, particularly of that in the 10-hydroperoxy group (b) introduction of an additional double bond by dehydrogenation (c) oxidation of a hydroxy group to keto (d) dehydration of a 9-H-11-OH grouping to D9(11) (e) dihalogenation to 9a,11b - dihalogeno, or hydroxy - halogenation to 9a-halogeno-11b-hydroxy, of such a D9(11)-double bond. As source of oxygen, there may be employed hematoporphyrin or azoisobutyronitrile. A 13-alkyl-5(10)-gonene-3-one starting compound may be obtained by a Birch reduction of the corresponding 3-methoxy-13-alkyl-1,3,5 (10)-gonatriene. A 3-keto-13-alkyl-5a-1(10)-gonene starting compound may be obtained by deconjugating e.g. with an alkali metal acetylide, a corresponding 3-keto-13-alkyl - 5a - 1(2) - gonene. A 13 - alkyl - 5a-1(10) -gonene - 3- ol - 17 - one starting compound is obtained by oxidation of a 13-alkyl-5a - 1(10) - gonene - 17b - ol - 3 - one to form the corresponding 13-alkyl-5a-1(10)-gonene-3,17-dione followed by selective reduction. Pharmaceutical compositions having antigonadal or androgenic/anabolic activity and containing the above novel compounds are administered in tablets, solutions and suspensions.